JPH0388811A - Copolymer of vinylidene fluoride and ethylene, manufacture of said copolymer and its use as adhesive - Google Patents
Copolymer of vinylidene fluoride and ethylene, manufacture of said copolymer and its use as adhesiveInfo
- Publication number
- JPH0388811A JPH0388811A JP20591890A JP20591890A JPH0388811A JP H0388811 A JPH0388811 A JP H0388811A JP 20591890 A JP20591890 A JP 20591890A JP 20591890 A JP20591890 A JP 20591890A JP H0388811 A JPH0388811 A JP H0388811A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- copolymer
- vinylidene fluoride
- ethylene
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920001577 copolymer Polymers 0.000 title claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 29
- 239000005977 Ethylene Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000853 adhesive Substances 0.000 title claims description 4
- 230000001070 adhesive effect Effects 0.000 title claims description 4
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 239000000088 plastic resin Substances 0.000 claims 1
- 239000007870 radical polymerization initiator Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 229920001897 terpolymer Polymers 0.000 description 11
- 230000003247 decreasing effect Effects 0.000 description 10
- -1 polyethylene Polymers 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920006029 tetra-polymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、フッ化ビニリデンと、重合性不飽和官能基を
有する少なくとも１種のモノマーとのコポリマーに関す
る。フッ化ビニリデンとコポリマーを生成するモノマー
の１種はエチレンである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to copolymers of vinylidene fluoride and at least one monomer having polymerizable unsaturated functional groups. One monomer that forms a copolymer with vinylidene fluoride is ethylene.
コポリマーは、フッ化ビニリデン及びエチレンに、場合
によって他の１種以上の重合性不飽和モノマーを加えて
高圧下で共重合することにより製造される。 フッ化ビ
ニリデンホモポリマーは、通常の溶媒に対する耐性があ
り、また他の大部分の熱可塑性樹脂、特にポリオレフィ
ンとは相溶性がないことで知られている。コポリマーに
よりフッ化ビニリデンポリマーの特性を、従来のポリマ
ー特にポリエチレンの特性と結び付けることができる。The copolymer is made by copolymerizing vinylidene fluoride and ethylene, optionally with one or more other polymerizable unsaturated monomers, under high pressure. Vinylidene fluoride homopolymers are known to be resistant to common solvents and to be incompatible with most other thermoplastics, especially polyolefins. Copolymers allow the properties of vinylidene fluoride polymers to be combined with those of conventional polymers, especially polyethylene.
従来の溶媒、例えば炭化水素に溶けるこのコポリマーは
、塗装、特に落書防止塗装での原樹脂として、また更に
は熱可塑性樹脂加工中の潤滑剤（加工助剤）として、中
でもポリフッ化ビニリデン又はそのコポリマーと、フッ
素含有樹脂とは不相溶性の他のプラスチック樹脂、特に
ポリオレフィン、中でも特にポリエチレンとの間の接着
用中間剤として使用することができる。This copolymer, which is soluble in conventional solvents such as hydrocarbons, can be used as base resin in coatings, especially anti-graffiti coatings, or even as a lubricant (processing aid) during the processing of thermoplastics, inter alia polyvinylidene fluoride or its copolymers. and other plastic resins that are incompatible with the fluorine-containing resin, especially polyolefins, especially polyethylene.
フッ化ビニリデンのこのランダムコポリマーは分子中に
、０．７〜３７重量％のフッ化ビニリデンと、９９．３
〜６３重量％の少なくとも１種の共重合化重合性不飽和
モノマーとを包含している。エチレンは少なくとも他の
１種の重合性不飽和モノマーと会合すると必ずフッ化ビ
ニリデンと共重合するはずなので、ランダムコポリマー
は一般にこの場合で、分子中に少なくとも２０重量％の
、好ましくは２０〜９５重量％の共重合化エチレンを包
含している。ポリフッ化ビニリデンホモポリマーの溶融
温度が生成物によって実質的に１５４℃〜１８４°Ｃで
変動し、またラジカルポリエチレン（ｐｏｌｙｌ！ｔｈ
ｙｌａｎｅｒａｄｉｃａｌａｉｒｅ）の溶融温度が約１
１４℃〜１１７℃のときに、本発明のコポリマーは一般
に４０℃〜１１３℃の融点を有する。溶融温度はコポリ
マーに含まれるフッ化ビニリデンの量に応じて変動する
。実質的に８５℃の溶融温度は、実質的に３７重量％の
残留フッ化ビニリデンを包含しているコポリマーに相当
し、実質的に１１３℃の溶融温度は実質的に０．７重量
％の残留フッ化ビニリデンを包含しているコポリマーに
相当する。このような状況では、これらの生成物はフッ
化ビニリデンホモポリマー及びエチレンホモポリマーよ
りも製造が簡単であるという利点を有する。This random copolymer of vinylidene fluoride contains 0.7 to 37% by weight of vinylidene fluoride and 99.3% by weight of vinylidene fluoride in the molecule.
~63% by weight of at least one copolymerizable unsaturated monomer. Since ethylene must copolymerize with vinylidene fluoride whenever it is associated with at least one other polymerizable unsaturated monomer, random copolymers generally have at least 20% by weight in the molecule, preferably 20-95% by weight. % copolymerized ethylene. The melting temperature of polyvinylidene fluoride homopolymers varies substantially between 154°C and 184°C depending on the product, and radical polyethylene (polyl!th
ylaneradicalaire) has a melting temperature of approximately 1
At 14°C to 117°C, the copolymers of the invention generally have a melting point of 40°C to 113°C. The melting temperature varies depending on the amount of vinylidene fluoride contained in the copolymer. A melting temperature of substantially 85°C corresponds to a copolymer containing substantially 37% by weight residual vinylidene fluoride, and a melting temperature of substantially 113°C corresponds to a copolymer containing substantially 37% by weight residual vinylidene fluoride. Corresponds to a copolymer containing vinylidene fluoride. In this situation, these products have the advantage of being easier to manufacture than vinylidene fluoride homopolymers and ethylene homopolymers.
高分子化合物が結晶質であればあるほど、融解熱は高く
なる。この融解熱は、２０℃／分の温度プログラミング
により使用されるＤＵ ＰＯＮＴ ＤＥＮＥＮＯＵＲＳ
製装置ＤＳＣ９９０により公知の方法で測定される１本
発明のコポリマーの融解熱は３０〜１２０Ｊ／ｇである
。比較として、ポリフッ化ビニリデンの融解熱は実質的
に５５Ｊ／ｇであり、ラジカルポリエチレンの融解熱は
実質的に１６２Ｊ／ｇである。The more crystalline the polymer, the higher the heat of fusion. This heat of fusion is used by DU PONT DENENOURS with temperature programming of 20°C/min.
The heat of fusion of one of the copolymers of the present invention, measured in a known manner with a manufacturing device DSC990, is from 30 to 120 J/g. By way of comparison, the heat of fusion of polyvinylidene fluoride is substantially 55 J/g and the heat of fusion of radical polyethylene is substantially 162 J/g.
コポリマーの重量平均分子量は３０，０００〜ｚｏｏ
、ｏｏｏであり、特に製造を簡単にするためには、重量
平均分子量が３５，０００〜１５０，０００のコポリマ
ーが好ましい、 Ｍｗ／Ｍｎ比（Ｍ−は重量平均分子量
であり、Ｍｎは数平均分子量である）に相当するコポリ
マーの多分散度は１．５〜５であり、好ましくは２〜４
である。The weight average molecular weight of the copolymer is 30,000~zoo
, ooo, and particularly for ease of production, copolymers with a weight average molecular weight of 35,000 to 150,000 are preferred, Mw/Mn ratio (M- is the weight average molecular weight, Mn is the number average molecular weight The polydispersity of the copolymer corresponding to
It is.
６・１０７ 〜３・１０８Ｐａ、好ましくは８・１０７
〜１．５・１０”Ｐａの圧力下で、超臨界媒質において
、少なくとも１種の第３のモノマーの存在下で又は不在
下でフッ化ビニリデンとエチレンとを共重合してコポリ
マーを製造する。6.107 to 3.108Pa, preferably 8.107
The copolymer is produced by copolymerizing vinylidene fluoride and ethylene in the presence or absence of at least one third monomer in a supercritical medium under a pressure of ˜1.5·10” Pa.
フッ化ビニリデンの臨界圧力及び臨界温度はそれぞれ実
質的に４４．３・１０７Ｐａ及び３０．１℃である。エ
チレンの場合はそれぞれ４９・１０７Ｐａ及び９．５℃
である。The critical pressure and critical temperature of vinylidene fluoride are substantially 44.3·107 Pa and 30.1° C., respectively. In the case of ethylene, it is 49・107Pa and 9.5℃, respectively.
It is.
一般にコモノマーは反応器内では気体状態で重合し、場
合によってはラジカル反応に係わる遊離基開始剤の存在
下で、窒素又はアルゴンのような不活性ガスで希釈され
る。ラジカル重合自体は知られており、開始剤は従来型
である。開始剤は通常、ブチルペルベンゾエートのよう
な有機過酸化物又はアゾ官能基を含む過酸化物の中から
選択する。開始剤／コモノマーのモル比は一般に１５〜
６０ｐｐ輪、好ましくは３０〜４５ｐｐｍである。Generally, the comonomer is polymerized in the gaseous state in the reactor and is diluted with an inert gas such as nitrogen or argon, optionally in the presence of a free radical initiator for the radical reaction. Radical polymerization itself is known and the initiators are conventional. The initiator is usually chosen among organic peroxides such as butyl perbenzoate or peroxides containing azo functionality. The initiator/comonomer molar ratio is generally from 15 to
60 ppm, preferably 30-45 ppm.
フッ化ビニリデンとエチレンとの混合物の重量に対して
計算された反応物（ｃｈａｒｇｅｒ！ａｃｔｉｏｎｎｅ
ｌｌｅ）中のフッ化ビニリデンの重量比は９〜８５％で
ある。このような反応物により、フッ化ビニリデンの質
量単位当たりの含有量（ｔｅｎｅｕｒｍａｓｓｉｑｕｅ
）が実質的に０．７〜３７％であるコポリマーを製造す
ることができる。第３のモノマーを加えるときに、反応
物中でのこのモノマーの量はフッ化ビニリデンとエチレ
ンとの混合物の５〜４０重量％、好ましくは８〜３０重
量％になる。The charge!actionne calculated for the weight of the mixture of vinylidene fluoride and ethylene.
The weight ratio of vinylidene fluoride in lle) is 9 to 85%. Such reactants reduce the content per mass unit of vinylidene fluoride.
) can be produced between substantially 0.7% and 37%. When adding the third monomer, the amount of this monomer in the reaction will be from 5 to 40%, preferably from 8 to 30% by weight of the mixture of vinylidene fluoride and ethylene.
共重合温度は使用する開始剤の分解温度を上回らねばな
らない０通常１００〜２５０℃のこの温度は、開始剤の
分解温度と、共重合の圧力で使用されるモノマーの熱分
解温度との間になければならない。The copolymerization temperature must be above the decomposition temperature of the initiator used. This temperature, usually between 100 and 250 °C, is between the decomposition temperature of the initiator and the thermal decomposition temperature of the monomers used at the copolymerization pressure. There must be.
モノマーと開始剤との混合物の温度が開始剤の分解温度
のときは、温度と圧力とは上昇し、共重合は急速に進行
する。所定の圧力では、反応速度は使用する開始剤の量
により決まる。最高反応温度に達するための反応時間は
数秒〜数分の間で変動し得る０反応時間自体は一般に４
０分を越えない。When the temperature of the mixture of monomer and initiator is at the decomposition temperature of the initiator, the temperature and pressure increase and copolymerization proceeds rapidly. At a given pressure, the rate of reaction is determined by the amount of initiator used. The reaction time to reach the maximum reaction temperature can vary between seconds and minutes; the reaction time itself is generally 4
Do not exceed 0 minutes.
共重合は連続的に又は断続的に行われ得る。連続的共重
合は、総ての高圧重合と同様に管状反応器で実施するこ
とができる。モノマーは同時に反応器内に導入する６反
応器に共重合温度を適用するのが好ましく、場合によっ
ては脂肪族炭化水素（ヘキサン又はへブタン）のような
不活性溶媒に溶解した滴定量の開始剤を使用する。生成
したポリマーを圧力調整バルブを使用して連続的に回収
することができる。好ましくは撹拌手段及び加熱・冷却
手段を備え、場合によって生成した粉末を回収するため
の分離回収器を備えている反応器で、断続的共重合を実
施することができる。断続的共重合では、場合によって
不活性溶媒に希釈した開始剤を徐々に加える前に、反応
器内において開始剤の分解温度を上回る温度でモノマー
を気体状態にすることが推奨される。温度を下げて減圧
した後に、生成したコポリマーを回収することができる
。Copolymerization can be carried out continuously or intermittently. Continuous copolymerization, like all high-pressure polymerizations, can be carried out in tubular reactors. It is preferable to apply a copolymerization temperature to 6 reactors in which the monomers are simultaneously introduced into the reactor and optionally a titrated amount of initiator dissolved in an inert solvent such as an aliphatic hydrocarbon (hexane or hebutane). use. The produced polymer can be continuously recovered using a pressure regulating valve. The intermittent copolymerization can be carried out in a reactor, preferably equipped with stirring means and heating and cooling means, optionally with a separator and collector for recovering the powder produced. In intermittent copolymerization, it is recommended to bring the monomer into the gaseous state in the reactor at a temperature above the decomposition temperature of the initiator before gradually adding the initiator, optionally diluted in an inert solvent. After lowering the temperature and applying vacuum, the formed copolymer can be recovered.
通常オレフィンの重合又は共重合で使用される高圧重合
は、爆発の危険性のある反応である。従って、温度及び
圧力の上昇を厳重にチエツクして大幅に抑制せねばなら
ない、更には、少なくとも反応器内の物質の急速排出用
及び圧力低下用装置を備えた、この種の反応に適合する
装置を使用する必要がある。特に、例えば重合成分導入
装置又は反応器の撹拌装置内では、公知の方法によりモ
ノマーを任意の潤滑剤と接触させないようにすることが
推奨される。The high pressure polymerization normally used in the polymerization or copolymerization of olefins is a potentially explosive reaction. Therefore, the rise in temperature and pressure must be strictly checked and significantly suppressed, and in addition, equipment suitable for this type of reaction must be provided, at least with devices for the rapid evacuation of the substances in the reactor and for reducing the pressure. need to be used. In particular, it is recommended to prevent the monomers from coming into contact with any lubricants by known methods, for example in the polymerization component introduction device or in the stirring device of the reactor.
重合反応速度が超過しないようにするために、例えば後
述する手段を単独で又は組み合わせて使用して、反応を
抑制することができる。In order to prevent the polymerization reaction rate from being exceeded, the reaction can be suppressed, for example by using the measures described below alone or in combination.
これらの手段の１つは使用する開始剤の量を、−ａに開
始剤の分解温度である初期反応温度と、共重合熱に起因
する発熱ピーク（ｐｉｅｄ’ ｅｘｏｔｈｅｒ＊１ｃｉ
ｔりにより達する温度との間の妥当な温度差（６４℃）
を得るのに必要な量に制限することである。この６４℃
は好ましくは１００℃未満である。少なくとも１回目の
共重合では、以後の共重合で使用すべき正確な量を決定
するために、開始剤を徐々に注入することが推奨され得
る。One of these means is to adjust the amount of initiator used so that -a is the initial reaction temperature, which is the decomposition temperature of the initiator, and the exothermic peak due to the heat of copolymerization.
A reasonable temperature difference (64°C) between the temperature reached by
The goal is to limit the amount necessary to obtain the desired amount. This 64℃
is preferably less than 100°C. At least for the first copolymerization, it may be recommended to gradually inject the initiator in order to determine the exact amount to be used in subsequent copolymerizations.
他の手段は、例えば反応器を冷却して熱量を排出するこ
とにより、反応温度を抑制することである。Another measure is to suppress the reaction temperature, for example by cooling the reactor and discharging the heat.
第３の手段は、重合中の反応混合物の圧力を多少部分的
に下げることである。この手段を使用するためには、反
応器に完全に適合する装置を備えることが推奨される。A third measure is to more or less partially reduce the pressure of the reaction mixture during polymerization. In order to use this means, it is recommended to equip the reactor with equipment that is completely compatible.
提起する装置は、はぼ−瞬にして排気し得るのに十分な
通過直径（ｄｉａｍａｔｒｅｓｄｅ ｐａｓｓａｇｅ）
を有する少なくとも２つの急速排気バルブを反応器の本
体の最も近くに装着している反応器である。The proposed device has a passage diameter sufficient to permit instantaneous evacuation.
The reactor is equipped with at least two quick exhaust valves having a diameter of at least two rapid exhaust valves closest to the body of the reactor.
好ましくはハロゲンのない第３のモノマーを少なくとも
１種、フッ化ビニリデンとエチレンとの混合物に加える
ことができる。この重合性不飽和モノマーは好ましくは
分子中に、１個の重合性二重結合を含んでいる。このモ
ノマーは通常、芳香族モノマー（スチレン系モノマー、
特にスチレン及びα−メチルスチレン等）、アリル系モ
ノマー（アリルアルコール等）、酸性モノマー又は不飽
和無水カルボン酸（無水マレイン酸又はマレイン酸等）
、α−オレフィン系モノマー（プロピレン、ブテン又は
ヘキセン等）、アクリル系モノマー（アクリル酸メチル
、アクリル酸エチル、メチルアクリル酸メチル又はメチ
ルアクリル酸エチル等）、ビニル系モノマー（酢酸ビニ
ル等〉の中から選択する。At least one third monomer, preferably halogen-free, can be added to the vinylidene fluoride and ethylene mixture. This polymerizable unsaturated monomer preferably contains one polymerizable double bond in the molecule. This monomer is usually an aromatic monomer (styrenic monomer,
In particular, styrene and α-methylstyrene), allyl monomers (allyl alcohol, etc.), acidic monomers or unsaturated carboxylic anhydrides (maleic anhydride or maleic acid, etc.)
, α-olefin monomers (propylene, butene, hexene, etc.), acrylic monomers (methyl acrylate, ethyl acrylate, methyl methyl acrylate or methyl acrylate, etc.), vinyl monomers (vinyl acetate, etc.) select.
第３のモノマーが重合に介在するときには、開始剤の分
解開始前ならいつでも、液体モノマーの場合には好まし
くはエチレンを加える前に、反応媒質中にこのモノマー
を導入することができる。When a third monomer intervenes in the polymerization, it can be introduced into the reaction medium at any time before the initiation of decomposition of the initiator, and in the case of liquid monomers, preferably before addition of ethylene.
液体モノマーの断続的重合の場合には、実際問題として
まず反応器内にフッ化ビニリデンを、次いで第３のモノ
マーを、最後にエチレンを導入するのが好ましい。連続
的重合の場合には、モノマーを同時に連続して注入する
のが好ましい。In the case of intermittent polymerization of liquid monomers, it is preferred in practice to first introduce the vinylidene fluoride into the reactor, then the third monomer and finally the ethylene. In the case of continuous polymerization, it is preferred to inject the monomers simultaneously and successively.
コポリマーを接着用中間剤として使用するときには、分
子中に７〜３５重量％の、好ましくは１０〜３０重量％
の残留フッ化ビニリデンと、３０〜７８重量％の、好ま
しくは４０〜６０ｆｆｉ量％の残留エチレンと、１０〜
５０重量％の、好ましくは１５〜３５重量％の少なくと
も１種の第３の残留重合性不飽和モノマーとを含んでい
るコポリマーが特に推奨される。When the copolymer is used as an adhesive intermediate, 7 to 35% by weight, preferably 10 to 30% by weight in the molecule.
of residual vinylidene fluoride, 30 to 78% by weight of residual ethylene, preferably 40 to 60% of residual ethylene, and 10 to 78% by weight of residual ethylene.
Particularly recommended are copolymers containing 50% by weight, preferably from 15 to 35% by weight, of at least one residual third polymerizable unsaturated monomer.
コポリマーの組成に加わる第３のモノマーは、前述した
モノマーの中から選択され得る。酢酸ビニル、又は酢酸
ビニルと他の重合性不飽和モノマーとの混合物が特に推
奨される。The third monomer that joins the composition of the copolymer may be selected from the monomers described above. Vinyl acetate or mixtures of vinyl acetate and other polymerizable unsaturated monomers are particularly recommended.
以下の実施例により本発明を非制限的に説明する。The following examples illustrate the invention in a non-limiting manner.
幻り倒」２
分離回収器と、撹拌器とを装着する、使用圧力が２８０
０バールで、１５０℃にサーモスタット制御された１１
の反応器を窒素パージした後に、空気が入らないように
して、その中に１０３．２５ｇの液体フッ化ビニリデン
、次いで４１３．２２ｇのエチレンを導入した。圧力を
訃１０７Ｐａに上昇させた。１１当たり２ｇのｔ−ブチ
ルベルベンゾエートを含むヘプタン溶液３５ｃｍ’を３
０秒で導入した。共重合反応が直ちに開始し、導入から
１分後には最高温度２２３℃に達した。即ち６１℃は７
３℃であった。最高圧力は１．３０５・１０”Ｐａに達
した。温度及び圧力はそれがら低下した。温度が初期温
度付近まで低下すると、減圧して、分離回収器内で５２
．７ｇの粉末形態のコポリマーを回収した。質量単位当
たりの転化率（ｔａｕｘ ｄａ ｃｏｎｖｅｒｓｉｏｎ
ｍａｓｓｉｑｕｅ）は１０．２％であった。``Genkita'' 2 Separator and recovery device and agitator are installed, working pressure is 280
11 thermostatically controlled at 150°C at 0 bar.
After the reactor was purged with nitrogen, 103.25 g of liquid vinylidene fluoride and then 413.22 g of ethylene were introduced into it without air. The pressure was increased to 107 Pa. 35 cm' of heptane solution containing 2 g of t-butylberbenzoate per 3
It was introduced in 0 seconds. The copolymerization reaction started immediately and reached a maximum temperature of 223°C one minute after introduction. In other words, 61℃ is 7
The temperature was 3°C. The maximum pressure reached 1.305・10"Pa. The temperature and pressure decreased accordingly. When the temperature decreased to around the initial temperature, the pressure was reduced and 52
．． 7 g of copolymer in powder form was recovered. conversion rate per mass unit
massique) was 10.2%.
このポリマーは融点が１１２．７℃であり、２．２８重
量％のフッ化ビニリデンを含んでいた。重量平均分子量
は１３９，０００であり、多分散度は３．５であった。This polymer had a melting point of 112.7°C and contained 2.28% by weight vinylidene fluoride. The weight average molecular weight was 139,000 and the polydispersity was 3.5.
融解熱は１１８Ｊ／ｇであった。The heat of fusion was 118 J/g.
及五透ユ
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に７００ｇの液体フッ化ビニリデン、
次いで１２２．８ｇのエチレンを、即ち８５．０６％が
フッ化ビニリデンの混合物を導入した。The inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 700 g of liquid vinylidene fluoride,
Then 122.8 g of ethylene, ie a mixture of 85.06% vinylidene fluoride, was introduced.
圧力を１０”Ｐａに上昇させた。１１当たり５ｇのｔ−
ブチルベルベンゾエートを含むヘプタン溶液２５ｃｍ”
を３０秒で導入した。共重合反応が直ちに開始し、２分
３０秒で最高温度１９２℃に達した。即ち６１℃は４２
℃であった。最高圧力は１．１５・１０”Ｐａに達した
。温度及び圧力はそれから低下した。温度が初期温度付
近まで低下すると、減圧して、分離回収器内で６１．９
ｇのコポリマーを回収した。即ち質量単位当たりの転化
率は７．５％であった。The pressure was increased to 10”Pa. 5g t- per 11
25cm of heptane solution containing butylberbenzoate
was introduced in 30 seconds. The copolymerization reaction started immediately and reached a maximum temperature of 192°C in 2 minutes and 30 seconds. That is, 61℃ is 42
It was ℃. The maximum pressure reached 1.15·10"Pa. The temperature and pressure then decreased. When the temperature decreased to around the initial temperature, the pressure was reduced to 61.9 Pa in the separator and collector.
g of copolymer were recovered. That is, the conversion rate per mass unit was 7.5%.
コポリマーは融点が８６．７℃であり、３６．８重量％
のフッ化ビニリデンを含んでいた６重量平均分子量は９
２，７００であり、多分散度は２．９３であった０ｗＡ
解熱は５Ｂ、３Ｊ／ｇであった。The copolymer has a melting point of 86.7°C and 36.8% by weight
The weight average molecular weight of 6 containing vinylidene fluoride was 9.
2,700 and the polydispersity was 2.93.
Antipyretic was 5B, 3J/g.
え見斑ｌ
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に２６０ｇの液体フッ化ビニリデン、
次いで６７．５ｇの酢酸ビニル、最後に３０７電のエチ
レンを導入した。圧力を１．１・１０７Ｐａに上昇させ
た。１２当たり１０ｇのｔ−ブチルベルベンゾエートを
含むヘプタン溶液８．５ｃ−を３０秒で導入した。The inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 260 g of liquid vinylidene fluoride,
Then 67.5 g of vinyl acetate and finally 307 g of ethylene were introduced. The pressure was increased to 1.1·107 Pa. 8.5 c of a heptane solution containing 10 g of t-butylberbenzoate per 12 hours was introduced in 30 seconds.
共重合反応が直ちに開始し、４０秒で最高温度２０２℃
に達した。即ち６１℃は５２℃であった。最高圧力は１
．１２・１０８Ｐａに達した。温度及び圧力はそれから
低下した。温度が初期温度付近まで低下すると、減圧し
て、分離回収器内で８２ｇのターポリマーを回収した。The copolymerization reaction starts immediately and reaches a maximum temperature of 202℃ in 40 seconds.
reached. That is, 61°C was 52°C. The maximum pressure is 1
．． It reached 12.108Pa. The temperature and pressure then decreased. When the temperature decreased to around the initial temperature, the pressure was reduced and 82 g of terpolymer was collected in a separator and collector.
即ち質量単位当たりの転化率は１３％であった。That is, the conversion rate per mass unit was 13%.
ターポリマーは融点が７６．７℃であり、１０．４重量
％のフッ化ビニリデンと、１３．３重量％の酢酸ビニル
とを含んでいた０重畳平均分子量は８６，０００であり
、多分散度は２．７であった。融解熱は５５．６Ｊ／ｇ
であった。The terpolymer had a melting point of 76.7°C, contained 10.4% by weight of vinylidene fluoride and 13.3% by weight of vinyl acetate, had a zero fold average molecular weight of 86,000, and a polydispersity of was 2.7. Heat of fusion is 55.6 J/g
Met.
Ｘ胤透１
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に２６０ｇのフッ化ビニリデン、次い
で１４ｇのメチルメタクリレート、最後に４０３ｇのエ
チレンを導入した。圧力を１・１０”Ｐａに上昇させた
。１１当たり５ｇのｔ−ブチルペルベンゾエートを含む
ヘプタン溶液１１ｃ１．４ｃ＋ｅ’、次いで４ｃ−を２
分間の間隔で連続して導入した。反応が開始し、開始剤
の３度目の注入から３分後に温度が１６８℃に上昇した
。６１℃は１８℃であった。最高圧力は１．４・１０”
Ｐａに達した。温度及び圧力はそれから低下した。温度
が初期温度付近まで低下すると、減圧して、分離回収器
内で６４ｇのターポリマーを回収した。即ち質量単位当
たりの転化率は９．４５％であった。X-Tane 1 The inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 260 g of vinylidene fluoride, then 14 g of methyl methacrylate, and finally 403 g of ethylene were introduced therein. The pressure was increased to 1·10"Pa. Heptane solution 11c1.4c+e' containing 5 g of t-butyl perbenzoate per 11, then 4c-
They were introduced continuously at intervals of minutes. The reaction started and the temperature rose to 168° C. 3 minutes after the third injection of initiator. 61°C was 18°C. Maximum pressure is 1.4・10"
It reached Pa. The temperature and pressure then decreased. When the temperature decreased to around the initial temperature, the pressure was reduced and 64 g of terpolymer was collected in a separator and collector. That is, the conversion rate per mass unit was 9.45%.
ターポリマーは融点が９７℃であり、１１．６重量％の
フッ化ビニリデンと、１４．１重量％のメチルメタクリ
レートとを含んでいた０重量平均分子量は５８．０００
であり、多分散度は２．３であった。融解熱は６３．Ｉ
Ｊ／ｇであった。The terpolymer had a melting point of 97°C and contained 11.6% by weight vinylidene fluoride and 14.1% by weight methyl methacrylate.The weight average molecular weight was 58.000.
The polydispersity was 2.3. The heat of fusion is 63. I
It was J/g.
実４日１至
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に３９５ｇのフッ化ビニリデン、次い
で６２．５ｇの酢酸ビニル、最後に１８７．５ｇのエチ
レンを導入した。圧力を１．０４・１０”Ｐａに上昇さ
せた。１１当たり５ｇのｔ−ブチルペルベンゾエートト
を含むヘプタン溶液１０ｃｍを３０秒で導入した０反応
がゆっくり開始し、６分で１６８℃の温度に達した。On the 4th day of the experiment, the inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 395 g of vinylidene fluoride, then 62.5 g of vinyl acetate, and finally 187.5 g of ethylene were added to the reactor. Introduced. The pressure was increased to 1.04·10"Pa. 10 cm of heptane solution containing 5 g of t-butyl perbenzoate per 11 was introduced in 30 seconds. The reaction started slowly and reached a temperature of 168 °C in 6 minutes. Reached.
即ち６１℃は１８℃であった。最高圧力は１．０５・１
０７Ｐａに達した。温度及び圧力はそれから低下した。That is, 61°C was 18°C. Maximum pressure is 1.05.1
It reached 0.07Pa. The temperature and pressure then decreased.
温度が初期温度付近まで低下すると、減圧して、分離回
収器内でＢｉｇのターポリマーを回収した。When the temperature decreased to around the initial temperature, the pressure was reduced and the Big terpolymer was collected in a separation and recovery vessel.
即ち質量単位当たりの転化率は９．５％であった。That is, the conversion rate per mass unit was 9.5%.
ターポリマーは融点が４０．１℃であり、１９．１重量
％のフッ化ビニリデンと、２１．８重量％の酢酸ビニル
とを含んでいた０重量平均分子量は３７，０００であり
、多分散度は２．４であった。融解熱は３１．６Ｊ／ｇ
であった。The terpolymer had a melting point of 40.1°C, contained 19.1% by weight of vinylidene fluoride and 21.8% by weight of vinyl acetate, had a weight average molecular weight of 37,000, and a polydispersity of was 2.4. Heat of fusion is 31.6 J/g
Met.
得られた生成物をポリフッ化ビニリデンとポリエチレン
との間の結合剤として使用した。厚さが１６０μ輪のポ
リエチレン切片と厚さが５０μ論のポリフッ化ビニリデ
ン切片との間に、前述したターポリマーを配置した。３
〜６・１０７Ｐａの圧力を１０秒間かけて全体を加熱接
着した。ターポリマー中間層を含む切片が得られた。全
体として１５０〜３００μ−の厚さを有していた。冷却
後に幅が１０間のバンドに切断し、その上で力畳計ｌＮ
５ＴＲＯＮを使用して皮膜除去試験を実施した。１３０
℃、１４０℃、１５０℃及び１６０℃の接着温度を使用
してこのような状況で製造した４種のサンプルの分速５
０間での皮膜除去結果は、それぞれ各サンプルで平均し
て１００ｇ／１０＋＊ｍ、１６０ｇ７１０ｍｍ、３４０
ｇ７１０ｍｍ及び５００ｇ７１０ｍｍであった。The resulting product was used as a binder between polyvinylidene fluoride and polyethylene. The above-mentioned terpolymer was placed between a polyethylene section having a thickness of 160 .mu.m and a polyvinylidene fluoride section having a thickness of 50 .mu.m. 3
The whole was heat-bonded by applying a pressure of ~6·107 Pa for 10 seconds. Sections containing a terpolymer interlayer were obtained. The overall thickness was 150-300 microns. After cooling, cut into bands with a width of 10 mm, and then apply a force meter on the band.
A film removal test was conducted using 5TRON. 130
The speed per minute of four samples produced under these conditions using bonding temperatures of 140°C, 150°C and 160°C
The average film removal results for each sample between
They were g710mm and 500g710mm.
Ｘ旌逍１
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に４３０．のフッ化ビニリデン、次い
で１０５ｇの酢酸ビニル、最後に１９５ｇのエチレンを
導入した。その時点で反応器内の圧力は１．０３・１０
”Ｐａであり、温度は１４７℃であった。１１当たり５
ｇのｔ−ブチルペルベンゾエートを含むヘプタン溶液１
２ｃｍを３０秒で導入した０反応が直ちに開始し、温度
が１５０秒で１７０℃に達した。即ちΔｔ’Ｃは２７℃
であった。X 旌逍1 The inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 430. of vinylidene fluoride, then 105 g of vinyl acetate and finally 195 g of ethylene were introduced. At that point, the pressure inside the reactor was 1.03.10
"Pa, and the temperature was 147°C. 5 per 11
g of t-butyl perbenzoate in heptane solution 1
The reaction started immediately when 2 cm was introduced in 30 seconds, and the temperature reached 170° C. in 150 seconds. That is, Δt'C is 27℃
Met.
最高圧力は１．１０・１０”Ｐａに達した。The maximum pressure reached 1.10·10"Pa.
温度が初期温度付近まで低下すると、圧力は８．５０・
１０テＰａまで低減した。When the temperature drops to around the initial temperature, the pressure increases to 8.50.
The pressure was reduced to 10 TePa.
反応器を減圧して、６２．のターポリマーを回収した。62. Depressurize the reactor. of terpolymer was recovered.
これは８．５％の最大転化率に相当していた。This corresponded to a maximum conversion of 8.5%.
ターポリマーは融点が４０．１℃であり、１３．０重量
％のフッ化ビニリデンと、２８．０！ｔｆｉ％の酢酸ビ
ニルとを含んでいた０重量平均分子量はｔｘｔ、ｏｏｏ
であり、多分散度は２．２であった。融解熱は３１．６
Ｊ／ｇであった。The terpolymer has a melting point of 40.1°C, 13.0% by weight of vinylidene fluoride, and 28.0% by weight of vinylidene fluoride. tfi% vinyl acetate and the weight average molecular weight was txt, ooo
The polydispersity was 2.2. Heat of fusion is 31.6
It was J/g.
得られた生成物をポリフッ化ビニリデンとポリエチレン
との間の結合剤として使用した。厚さが１６０μ−のポ
リエチレン切片と厚さが５０μｍのポリフッ化ビニリデ
ン切片との間に、前述したターポリマーを配置した。３
〜６・１０５の圧力を１０秒間かけて全体を加熱接着し
た。厚さが２５０〜３００ｇｍの単一の切片が得られた
。冷却後に幅が１Ｏｎ＋ｍのバンドに切断し、その上で
力量計ｒＮｓＴＲＯＮを使用して皮膜除去試験を実施し
た。The resulting product was used as a binder between polyvinylidene fluoride and polyethylene. The terpolymer described above was placed between a 160 μm thick polyethylene section and a 50 μm thick polyvinylidene fluoride section. 3
The whole was heat-bonded by applying a pressure of ~6.105 for 10 seconds. A single section with a thickness of 250-300 gm was obtained. After cooling, it was cut into bands with a width of 1 On+m, and then a film removal test was conducted using a dynamometer rNsTRON.
１５０℃及び１８０℃の接着温度を使用してこのような
状況で製造した２種のサンプルの分速５０輸輪での皮膜
除去結果は、それぞれ各サンプルで平均して＞ １５０
０ｇ／ａｍ及び６００ｇ１ｃ論であった。前者の場合、
ポリエチレン膜が破壊しなければ複合体が解離し得ない
程度の接着であった。The film removal results for two samples produced under these conditions using bonding temperatures of 150°C and 180°C at a speed of 50 cycles per minute averaged > 150° for each sample, respectively.
It was 0g/am and 600g1c theory. In the former case,
The adhesion was such that the composite could not be dissociated unless the polyethylene film was destroyed.
及族透ｌ
実施例１の反応器内を窒素パージして空気が入らないよ
うにして、その中に４５５ｇのフッ化ビニリデン、次い
で５５．の酢酸ビニルを導入し、そこに０．０５ｇの無
水マレイン酸と、最後に２１１ｇのエチレンとを加えて
溶解した。その時点で反応器内の圧力は１．００・１０
”Ｐａであり、温度は１５０℃であった。１１当たり１
０ｇのｔ−ブチルペルベンゾエートを含むヘプタン溶液
１３ｃｍ’を３０秒で導入した。反応が直ちに開始し、
温度が１０５秒で２１７℃に上昇した。即ちΔｔ℃は６
７℃であった。ｉ＆高圧力は１．２２・１０・Ｐａに達
した。温度が初期温度付近まで低下すると、圧力は８．
７５・１０７Ｐａまで低減した。反応器を減圧して、４
３ｇのテトラポリマーを回収した。これは６％の最大転
化率に相当していた。The inside of the reactor of Example 1 was purged with nitrogen to prevent air from entering, and 455 g of vinylidene fluoride was added thereto, followed by 55 g of vinylidene fluoride. of vinyl acetate was introduced, and 0.05 g of maleic anhydride and finally 211 g of ethylene were added and dissolved therein. At that point, the pressure inside the reactor was 1.00.10
"Pa, and the temperature was 150°C. 1 per 11
13 cm' of a heptane solution containing 0 g of tert-butyl perbenzoate was introduced in 30 seconds. The reaction starts immediately,
The temperature rose to 217°C in 105 seconds. That is, Δt°C is 6
The temperature was 7°C. The i&high pressure reached 1.22·10·Pa. When the temperature drops to around the initial temperature, the pressure increases to 8.
The pressure was reduced to 75.107Pa. Depressurize the reactor and
3g of tetrapolymer was recovered. This corresponded to a maximum conversion of 6%.
テトラポリマーは融点が６４．６℃であり、２２．２重
量％のフッ化ビニリデンと、１５．２重量％の酢酸ビニ
ルと、０．０８重量％の無水マレイン酸とを含んでいた
。The tetrapolymer had a melting point of 64.6° C. and contained 22.2% by weight vinylidene fluoride, 15.2% by weight vinyl acetate, and 0.08% by weight maleic anhydride.
重量平均分子量は８５，０００であり、多分散度は３で
あった。The weight average molecular weight was 85,000 and the polydispersity was 3.
融解熱は５７．３Ｊ／ｇであった。The heat of fusion was 57.3 J/g.
Claims (18)
る少なくとも１種のモノマーとのコポリマーであって、
モノマーの１種がエチレンであることを特徴とするコポ
リマー。(1) A copolymer of vinylidene fluoride and at least one monomer having a polymerizable unsaturated functional group,
A copolymer characterized in that one of the monomers is ethylene.
と、９９．３〜６３重量％の少なくとも１種の共重合化
重合性不飽和モノマーとを含んでいることを特徴とする
請求項１に記載のコポリマー。(2) A claim characterized in that the molecule contains 0.7 to 37% by weight of vinylidene fluoride and 99.3 to 63% by weight of at least one copolymerizable unsaturated monomer. Copolymer according to item 1.
共重合化モノマーを含んでいることを特徴とする請求項
１又は２に記載のコポリマー。(3) The copolymer according to claim 1 or 2, further comprising a third copolymerizable monomer selected from polymerizable unsaturated monomers.
でいることを特徴とする請求項１から３のいずれか一項
に記載のコポリマー。(4) A copolymer according to any one of claims 1 to 3, characterized in that it contains at least 20% by weight of copolymerized ethylene.
ル系若しくはメタクリル系モノマーであることを特徴と
する請求項１から４のいずれか一項に記載のコポリマー
。(5) The copolymer according to any one of claims 1 to 4, wherein the third copolymerizable monomer is vinyl acetate or an acrylic or methacrylic monomer.
であることを特徴とする請求項１から５のいずれか一項
に記載のコポリマー。(6) Weight average molecular weight is 30,000 to 200,000
Copolymer according to any one of claims 1 to 5, characterized in that it is.
請求項１から６のいずれか一項に記載のコポリマー。(7) The copolymer according to any one of claims 1 to 6, having a melting point of 40°C to 113°C.
する請求項１から７のいずれか一項に記載のコポリマー
。(8) The copolymer according to any one of claims 1 to 7, having a heat of fusion of 30 to 120 J/g.
求項１から８のいずれか一項に記載のコポリマー。(9) Copolymer according to any one of claims 1 to 8, characterized in that the polydispersity is 1.5-5.
リデンと、エチレン系不飽和官能基を有する少なくとも
１種のコモノマーとの共重合による、請求項１から８の
いずれか一項に記載のコポリマーの製造方法であって、
フッ化ビニリデンを６・１０＾７Ｐａ〜３・１０＾８Ｐ
ａの圧力下で少なくともエチレンと超臨界媒質で共重合
することを特徴とする製造方法。(10) The method according to any one of claims 1 to 8, by copolymerization of vinylidene fluoride and at least one comonomer having an ethylenically unsaturated functional group in the presence of a radical polymerization initiator. A method for producing a copolymer, the method comprising:
Vinylidene fluoride from 6.10^7Pa to 3.10^8P
A production method characterized by copolymerizing at least ethylene and a supercritical medium under the pressure of (a).
に対して計算された反応物中のフッ化ビニリデンの重量
比が９〜８５重量％であることを特徴とする請求項１０
に記載の製造方法。(11) Claim 10 characterized in that the weight ratio of vinylidene fluoride in the reactant is 9 to 85% by weight, calculated based on the weight of the mixture of vinylidene fluoride and ethylene.
The manufacturing method described in.
から選択された第３のモノマーを反応物中に加えること
を特徴とする請求項１０又は１１に記載の製造方法。(12) The production method according to claim 10 or 11, characterized in that a third monomer selected from polymerizable unsaturated monomers that do not contain halogen is added to the reaction product.
４０重量％の量の第３のモノマーを反応物に加えること
を特徴とする請求項１０から１２のいずれか一項に記載
の製造方法。(13) 5-5 of a mixture of vinylidene fluoride and ethylene
13. Process according to any one of claims 10 to 12, characterized in that an amount of 40% by weight of the third monomer is added to the reactants.
圧力での使用されるモノマーの熱分解温度との間にある
ことを特徴とする請求項１０から１３のいずれか一項に
記載の製造方法。(14) The copolymerization temperature is between the decomposition temperature of the initiator and the thermal decomposition temperature of the monomers used at the copolymerization pressure. Manufacturing method described.
熱に起因する発熱ピークにより達する温度との間の温度
差が１００℃未満になるように、使用する開始剤の量を
設定することを特徴とする請求項１０から１４のいずれ
か一項に記載の製造方法。(15) During the copolymerization reaction, the amount of initiator used is set so that the temperature difference between the decomposition temperature of the initiator and the temperature reached by the exothermic peak due to the heat of copolymerization is less than 100 °C. The manufacturing method according to any one of claims 10 to 14, characterized in that:
マーの中から選択された、ポリフッ化ビニリデン又はそ
のコポリマーと、フッ素含有樹脂と相溶性のないプラス
チック樹脂との間の接着用中間剤。(16) An intermediate agent for adhesion between polyvinylidene fluoride or its copolymer selected from the copolymers according to any one of claims 1 to 9 and a plastic resin that is incompatible with the fluorine-containing resin. .
フッ化ビニリデンと、３０〜７８重量％の残留エチレン
と、１０〜５０重量％の少なくとも１種の第３の残留重
合性不飽和モノマーとを含んでいることを特徴とする請
求項１６に記載の接着用中間剤。(17) The copolymer contains in the molecule 7 to 35% by weight of residual vinylidene fluoride, 30 to 78% by weight of residual ethylene, and 10 to 50% by weight of at least one residual third polymerizable unsaturated monomer. The adhesive intermediate agent according to claim 16, comprising:
ることを特徴とする請求項１７に記載の接着用中間剤。(18) The adhesive intermediate agent according to claim 17, wherein the third polymerizable unsaturated monomer is vinyl acetate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8910478 | 1989-08-03 | ||
| FR8910478A FR2650593B1 (en) | 1989-08-03 | 1989-08-03 | COPOLYMER OF VINYLIDENE AND ETHYLENE FLUORIDE AND PROCESS FOR OBTAINING SAME |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0388811A true JPH0388811A (en) | 1991-04-15 |
Family
ID=9384442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20591890A Pending JPH0388811A (en) | 1989-08-03 | 1990-08-02 | Copolymer of vinylidene fluoride and ethylene, manufacture of said copolymer and its use as adhesive |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0411990A1 (en) |
| JP (1) | JPH0388811A (en) |
| CA (1) | CA2022565A1 (en) |
| FI (1) | FI903851A0 (en) |
| FR (1) | FR2650593B1 (en) |
| NO (1) | NO903216L (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100548736B1 (en) * | 2001-10-17 | 2006-02-02 | 카도 인더스트리얼 컴파니 리미티드 | Collapsible Container |
| JP5092184B2 (en) * | 1999-02-15 | 2012-12-05 | ダイキン工業株式会社 | Method for producing fluoropolymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1191042A1 (en) * | 2000-09-26 | 2002-03-27 | Atofina | Process for polymerisation of 1,1difluoroethylen at high pressure |
| CN112375169B (en) * | 2020-07-31 | 2022-08-02 | 万向一二三股份公司 | Method for synthesizing binder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2468054A (en) * | 1944-02-28 | 1949-04-26 | Du Pont | Copolymers of vinylidene fluoride with ethylene and halogenated ethylenes |
| JPS4932786A (en) * | 1972-07-27 | 1974-03-26 | ||
| JPS59226410A (en) * | 1983-06-04 | 1984-12-19 | 呉羽化学工業株式会社 | Polymer dielectric material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2462678A (en) * | 1944-08-09 | 1949-02-22 | Du Pont | Catalysts for polymerizing olefins |
| US3449305A (en) * | 1966-03-01 | 1969-06-10 | Du Pont | Interpolymers of vinylidene fluoride |
| DE2037028C2 (en) * | 1970-07-25 | 1982-07-08 | Hoechst Ag, 6000 Frankfurt | Process for the production of fluorine-containing copolymers |
| US4123602A (en) * | 1976-05-24 | 1978-10-31 | Asahi Glass Company, Ltd. | Terpolymers of tetrafluoroethylene, ethylene and perfluoroalkyl vinyl monomer and process for producing the same |
-
1989
- 1989-08-03 FR FR8910478A patent/FR2650593B1/en not_active Expired - Fee Related
-
1990
- 1990-07-18 NO NO90903216A patent/NO903216L/en unknown
- 1990-07-24 EP EP19900402123 patent/EP0411990A1/en not_active Ceased
- 1990-08-02 FI FI903851A patent/FI903851A0/en not_active IP Right Cessation
- 1990-08-02 JP JP20591890A patent/JPH0388811A/en active Pending
- 1990-08-02 CA CA 2022565 patent/CA2022565A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2468054A (en) * | 1944-02-28 | 1949-04-26 | Du Pont | Copolymers of vinylidene fluoride with ethylene and halogenated ethylenes |
| JPS4932786A (en) * | 1972-07-27 | 1974-03-26 | ||
| JPS59226410A (en) * | 1983-06-04 | 1984-12-19 | 呉羽化学工業株式会社 | Polymer dielectric material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5092184B2 (en) * | 1999-02-15 | 2012-12-05 | ダイキン工業株式会社 | Method for producing fluoropolymer |
| KR100548736B1 (en) * | 2001-10-17 | 2006-02-02 | 카도 인더스트리얼 컴파니 리미티드 | Collapsible Container |
Also Published As
| Publication number | Publication date |
|---|---|
| NO903216L (en) | 1991-02-04 |
| FR2650593A1 (en) | 1991-02-08 |
| FI903851A0 (en) | 1990-08-02 |
| CA2022565A1 (en) | 1991-02-04 |
| NO903216D0 (en) | 1990-07-18 |
| EP0411990A1 (en) | 1991-02-06 |
| FR2650593B1 (en) | 1993-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4617366A (en) | Process for manufacturing ethylene terpolymers and ethylene copolymers | |
| EP0866810A1 (en) | Bulk radical polymerization using a batch reactor | |
| EP0463761B1 (en) | Copolymerization of ethylene with carbon monoxide and a comonomer | |
| US3132124A (en) | Copolymerization of tetrafluoroethylene and hexafluoropropylene | |
| CA2121705A1 (en) | Method of making a copolymer useful as viscosity index improving additive for hydraulic fluid | |
| JP3103576B2 (en) | Method for producing polyethylene and copolymer from main content of ethylene | |
| Liu et al. | Living/controlled copolymerization of acrylates with nonactivated alkenes | |
| CN111484576B (en) | Ethylene- (meth) acrylic acid copolymer and water-dispersible composition comprising the same | |
| KR890004327B1 (en) | Process for preparing latex polymers from gaseous monomer | |
| DE58903258D1 (en) | METHOD FOR LOW PRESSURE COPOLYMERIZATION OF ETHYLENE WITH ALPHA OLEFINES AND ETHYLENE COPOLYMERISATE WITH A LOW RESIDUAL MONOMER CONTENT. | |
| JPH0388811A (en) | Copolymer of vinylidene fluoride and ethylene, manufacture of said copolymer and its use as adhesive | |
| JPH06872B2 (en) | Ethylene copolymer aqueous dispersion | |
| US6245864B1 (en) | Copolymer of (a) ethylene and (b) and alkenoic acid or a derivative thereof a mixture of said monomers | |
| CA1275544C (en) | Omega-perfluoroalkyl-alpha-olefin polymers | |
| TWI721476B (en) | Vitrimer and preparation method thereof | |
| JP3370353B2 (en) | Ethylene homopolymer and copolymer | |
| Ramos et al. | Polymers from pine gum components: Radical and coordination homo and copolymerization of pinenes | |
| JPH02255884A (en) | Modified ethylene copolymer for adhesive | |
| US5328971A (en) | Copolymers of epoxybutadiene and maleimides | |
| JPH07258349A (en) | Copolymer of ethylene or ethylene derivative with fluorinated (meth)acrylate, its production, and its application | |
| JP2792982B2 (en) | Method for producing ethylene copolymer | |
| AU2932900A (en) | Isobutene polymerisation process | |
| JPH06279513A (en) | Preparation of low-molecular-weight ethylene - vinyl acetate copolymer | |
| JPS6050812B2 (en) | Method of producing ethylene copolymer | |
| Urushido et al. | Polymerization of allyl esters of unsaturated acids. IV. Cyclopolymerization of diallyl maleate |